Orbital-Optimized Quasi-Variational Distinguishable Cluster Doubles Method

Abstract

We present the orbital-optimized quasi-variational distinguishable cluster doubles (OQVDCD) method, obtained by applying the distinguishable cluster (DC) approximation to orbital-optimized quasi-variational coupled cluster doubles (OQVCCD). The resulting method retains a Hermitian-like energy functional, is size-extensive, obeys the generalized Hellmann-Feynman theorem at a stationary point, is exact in the isolated two-electron and two-hole limits, and scales as O(o2v4), like coupled cluster singles and doubles (CCSD). For the tested closed-shell reaction energies, it is shown that OQVDCD reduces the mean absolute deviation relative to OQVCCD from 1.20 to 0.81 kcal/mol, bringing the errors close to distinguishable cluster singles and doubles (DCSD). In the strongly correlated examples considered here, OQVDCD shifts the OQVCCD energies toward the benchmark, although the convergence remains somewhat less robust than for DCSD.